RESULTS AND DISCUSSION
4.3 BINARY SOLVENT EXTRACTION
4.3.2 Combination of Solvent Extraction
Since the optimal FASEs purity attainable after water-acetone extraction (water:acetone = 20:80, v/v) is about 88.81% with 68.85% recovery, the combination of water-acetone extractions were proposed to obtain higher purity and recovery as shown in Figure 3.6. After subjecting the
third fraction of NPLF to solvent extraction, three FASEs fractions could be obtained in different purities, i.e. 96.55% (23.20 % recovery), 86.82% (56.16% recovery), and 70.78% (13.32%
recovery), by using mixture of solvents with water to acetone volume ratios of 0/100, 10/90, and 20/80, respectively, as can be seen in Table 4-15.
Table 4-14 Comparison of results obtained by solvent extraction and distillation operated on the
3rd fraction of NPLF. a The composition of 3rd fraction NPLF of SODD sample IV is shown in Table 4-13.a Average of three independent experiments
b Content, wt.%
c Recovery = {(Fraction mass, g x content of the compound in Fraction, %) / (The 3rd fraction of NPLF mass, g x content of the compound in the 3rd fraction of NPLF, %)} x 100 %
d Mainly acylgycerols
Table 4-15 Precipitation fractions obtained by combined solvent extraction operated on the
3rd fraction of NPLF. aThe composition of 3rd fraction NPLF of SODD sample IV is shown in Table 4-15.
a Average of three independent experiments
b Content, wt.%
c Recovery = {(Fraction mass, g x content of the compound in Fraction, %) / (The 3rd fraction of NPLF mass, g x content of the compound in the 3rd fraction of NPLF, %)} x 100 %
d Mainly acylgycerols
e Amount = (Precipitate mass, g / the 3rd fraction of NPLF mass, g) x 100 %.
Steroidal hydrocarbons FASEs FFAs
Squalene Squalene A
E D C B
0 5 10 15 20 25 Retention time, minute
Flame Ionization Detector response, mV
Figure 4-4 HT-GC chromatograms. (A) SODD sample IV, (B) NPLF, (C) the 3
rd fraction from modified silica gel column chromatography, (D) the precipitation fraction from solvent extraction (water:acetone = 20:80, v/v), and (E) the supernatant fraction from solvent extraction.CHAPTER 5
CONCLUSIONS
The development of the effective isolation/fractionation method is important for lipid industries. The objective of this research is to develop economically viable techniques for the separation and purification of squalene, fatty acid steryl esters, tocopherols and phytosterols from soybean oil deodorizer distillate (SODD).
The first sub aim of the present study is to separate SODD into two fractions based on differences in the polarity of the constituent compounds. A modified soxhlet extraction was applied on SODD to obtain one fraction enriched with FASEs and squalene, while tocopherols, free phytosterols, TAGs, and FFAs were enriched in another fraction. Unlike classical soxhlet extraction, in modified soxhlet extractor, the extractor is equipped with a jacket to control the temperature of extraction chamber. The sample (SODD) in modified soxhlet extraction is coated onto silica gel The basic principle of separation in this new design can be understood in terms of the coating and selective desorption processes. Coating is a process that occurs when SODD accumulates on the surface of a silica gel, forming a thin film. Selective desorption occurs when some compounds in SODD that is coated on the surface of silica gel dissolve in hexane. The effectiveness of this separation was confirmed in subsequent experiments, carried out under the same conditions except with different SODD compositions (sample I, II, III and IV). From results obtained in this study, it can be seen that modified soxhlet extraction, which is much easier to operate than molecular distillation, can concentrate hydrocarbons and FASEs into NPLF.
Moreover, it operates under atmospheric pressure and lower temperature, and requires less sophisticated equipment. This method is capable to recover squalene and FASEs from SODD by 100% and 89.07 – 97.33%, respectively. Also, this method is capable of eliminating tocopherols, free phytosterols, FFAs, and acylglcerols from SODD by 87.99 – 95.68%, 97.26 – 99.76%, 76.13 – 82.11%, and 91.03 – 97.25%, respectively.
The second sub aim of this study is to evaluate the use of classical silica gel column chromatography during isolation of squalene and FASEs from NPLF. A new silica gel column chromatography was designed with the objective of greatly reducing the amount of solvent required to achieve the same degree of separation as the classical silica gel column chromatography. Unlike classical column chromatography, in this new design, glass tube was equipped with a jacket, a valve to control flow rate of eluent, a condenser system and a heating mantle. Although a heater is placed in the bottom part, a uniform temperature in the silica gel packing is achieved by maintaining the mobile phase volume at constant value. This design can be used either as soxhlet extraction or column chromatography by setting the valve. As the result, modified silica gel column chromatography process is feasible from economic point of view as compare to classical silica gel column chromatography because it significantly reduces the amount of solvent (< 1/73) and time required (< 1/18) to achieve the same degree of separation.
This new design is capable to recover squalene and FASEs from NPLF by 84.53 – 96.25%
(98.11-99.49% purity) and 93.52 – 100% (75.51 – 84.47% purity), respectively.
Another sub-purpose of this work is to isolate and purify natural fatty acids steryl esters (FASEs) from SODD by alternative method without degradation of FASEs. Molecular distillation was by far the preferred method to isolate FASEs from SODD. However it requires operation under high temperature and high vacuum with expensive equipment. Water-acetone extraction was employed on FASEs-rich fraction obtained by modified silica gel column chromatography.
This method gives better separation of FASEs with higher purity and recovery when applied to lipid fraction with high initial FASEs contents, and low contents of acylglycerols and hydrocarbons. The energy cost for the solvent recovery would be economically feasible because acetone does not form an azeotrope with water. Modified soxhlet extraction, modified silica gel column chromatography, and binary solvent extraction were employed sequentially in this study to obtain FASEs with three different purities, i.e. 96.55% (20.89 % total recovery), 86.82%
(50.57% total recovery), and 70.78% (11.99% total recovery) from SODD sample IV.
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會議名稱：
時間：August 24-28, 2008 地點：Prague, Czech Republic
主辦單位：Czech Society of Chemical Engineering
18th International Congress on Chemical and Process Engineering 為大型國際化工會議，由於研 討會主題幾乎涵蓋所有化工工程重要領域，如reaction engineering, separation process, systems and technology, hydrodynamic processes, system engineering and poster session；加上舉
行地點為人文薈萃、重要觀光旅遊景點之捷克首都布拉格，因此從66 個國家共有 1169 人
參加，非常踴躍。台灣有17 篇論文發表，來自台大、台灣科大、淡江大學、元智大學、清
華、逢甲、中原及長庚等大學。會議期間共五天。第一天為報到註冊及歡迎茶會，其後四 天研討會會正式上場。在口頭報告部分計有?個 session，總共有?篇論文。本人之論
文 ”Isolation and Identification of Aliphatic Hydrocarbons in Soybean Oil Deodorizer Distillate”
被安排在第二天session，由博士班學生申娜薇發表。除口頭報告論文外，另外還有?篇壁報
論文發表。